CN110684135A - Itaconic acid modified photoinitiator and preparation method thereof - Google Patents
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 52
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- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims abstract description 9
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
Abstract
The invention relates to an itaconic acid modified photoinitiator and a preparation method thereof, wherein the molecular formula of the itaconic acid modified photoinitiator is C29H34O10Specifically, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (Darocure 2959, HHMP) and Itaconic Acid (IA) are used as raw materials, and a polymerizable photoinitiator containing an itaconic acid unsaturated double bond structure is prepared through direct esterification reaction. The itaconic acid modified photoinitiator prepared by the invention takes 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone as a substrate, has good photoinitiation efficiency, and simultaneously, due to the introduction of itaconic acid groups, the new initiator has a polymerizable unsaturated double bond which is polymerized by photoinitiationCan participate in the polymerization of the system in the process, and obviously reduces the mobility of the residual photoinitiator.
Description
Technical Field
The invention relates to an itaconic acid modified photoinitiator and a preparation method thereof, and particularly belongs to the technical field of fine chemical engineering.
Technical Field
Photocuring refers to a process in which a liquid formulation material is instantaneously converted into a crosslinked solid state under the irradiation of ultraviolet light. The formulation materials typically include resins, reactive diluents, photoinitiators and other adjuvants. The photocuring technology has the advantages of fast curing, high production efficiency, energy conservation, environmental protection, economy, suitability for various substrates and the like, is widely applied to the fields of coatings, printing ink, adhesives, photoresists, rapid photo-forming materials, biomedical materials and the like, and along with the development of the photocuring technology, more and better photocuring products are developed, and the application field of the photocuring technology is wider.
The essence of photocuring is that the photoinitiator is rapidly decomposed under the radiation of ultraviolet light to generate active free radical fragments, and the photocuring resin and the active diluent are initiated to be polymerized and crosslinked instantly. The general content proportion of the photoinitiator is 1-5%, although the proportion is small, the effect of the photoinitiator is very critical. The photoinitiator plays a decisive role in the photocuring speed of the photocured product as an important part in the photocuring system. Among various photoinitiators, 1173 is one of widely used photoinitiators due to its characteristics of good initiation effect, no yellowing, simple structure, easy synthesis, low price, and the like. In the photo-curing process, the photo-curing agent has good compatibility with other materials, and is widely applied to various industries such as printing ink, paint, cosmetics and the like. Like most organic small molecule compounds, the compounds have certain toxicity to a greater or lesser extent, and particularly in the field of packaging and printing of foods, medicines, sanitary products and the like, after photocuring is completed, a part of photoinitiators are physically sandwiched in an acrylate cross-linked network to become residual photoinitiators, and when the photoinitiators are contacted with substances such as hot water, solvents, grease and the like, migration, permeation or extraction of molecules occurs, so that certain health safety hazards are caused. In order to solve the above problems, various technical methods have been reported in domestic and foreign research and development, and mainly include polymerizable photoinitiators and macromolecular photoinitiators. The copolymerizable photoinitiator is formed by connecting molecules with photoinitiation activity with polymerizable vinyl groups or epoxy groups and the like, and when photocuring crosslinking is carried out, the residual photoinitiator or cracking fragments participate in copolymerization and are connected and fixed in a crosslinking network to form a chemical unit which cannot be freely migrated, so that potential health and safety problems are inhibited. But the polymerization conversion rate in the polymerization process is difficult to reach 100 percent, certain polymerization residues always exist, and the sanitation potential safety hazard still exists. The characteristic that the molecular weight of the macromolecular photoinitiator is larger reduces the migration permeability of the residual photoinitiator, the molecular weight is usually 500-10000, and modifying the micromolecular photoinitiator into the macromolecular polymerizable photoinitiator with lower migration is an important development direction of the current photoinitiator, for example, the macromolecular benzophenone photoinitiator developed by the latest Junnie et al (synthesis and performance research [ J ], image science and photochemistry, 2019, 37(5), 445-plus 456), and the migration rate is 40% of the micromolecular photoinitiator.
Since the 21 st century, the world's demand for eco-friendly and sustainable energy has become increasingly urgent. Itaconic acid is a small molecule compound with unsaturated double bonds and terminal carboxyl groups, and Itaconic Acid (IA) has been promulgated by the national renewable Energy laboratories of the United states as one of the first twelve renewable Chemicals available for biomass due to its scalability, sustainability and nontoxicity (Werp T.; Petersen G. Top Value Added Chemicals from biological. Vol. I-Results of Screening for Potential Candidates from surfactants and Synthesis Gas; DOE/GO-102004-.
In the field of photocuring technology, many studies on polymerizable monomers (such as acrylic acid) obtained from traditional mineral raw materials as photoinitiator modified materials have been reported, and the research group has also applied for related patent (CN201610302241.0), but no studies on the use of itaconic acid containing double bonds as a modified photoinitiator material have been reported at home and abroad. The itaconic acid is known as methylene succinic acid and itaconic acid, is the fifth organic acid (the first four sites are citric acid, gluconic acid, lactic acid and malic acid in sequence) in the world, and is an unsaturated dibasic organic acid. The itaconic acid is regarded as a biomass renewable raw material, and is obtained by filtering, concentrating, decoloring, crystallizing and drying after fermenting for two days by mainly using agricultural and sideline products such as starch, cane sugar, molasses, wood chips, straw and the like as raw materials and using aspergillus terreus as a strain. According to the invention, the biological material itaconic acid is combined with the photoinitiator of a photocuring system, and the novel itaconic acid modified photoinitiator is prepared by utilizing the fact that the photoinitiator contains two carboxyl groups and an unsaturated double bond, and the photoinitiator can be used for inducing the mobility of residual small molecules of the photocuring system to be obviously reduced, and has the advantages of obvious low mobility and low volatility.
Disclosure of Invention
The invention aims to provide an itaconic acid modified photoinitiator and a preparation method thereof, which are based on a commercialized photoinitiator Darocure2959(2 hydroxy-4- (2 hydroxyethoxy) -2-methyl propiophenone, HHMP for short) with low toxicity, and the novel photoinitiator containing an initiating group and a polymerizable group is prepared by combining the hydroxyl on the molecule with the carboxyl of an itaconic acid molecule.
The molecular structure of the itaconic acid modified photoinitiator is as follows:
the preparation method of the itaconic acid modified photoinitiator comprises the following steps:
itaconic acid and photoinitiator 2 hydroxy-4- (2 hydroxyethoxy) -2-methyl propiophenone are taken as raw materials, and the itaconic acid modified photoinitiator with a polymerizable structure is synthesized through esterification reaction, and the method comprises the following specific steps:
in N2Under protection, respectively adding itaconic acid, hydroquinone of a polymerization inhibitor and a solvent N, N-dimethylformamide into a dry three-neck flask provided with a condenser pipe, a water separator and a thermometer, adding 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone after the itaconic acid is completely dissolved, stirring uniformly, continuously adding a catalyst of methanesulfonic acid, and keeping the temperature for continuously heating and reacting for 6 hours after the temperature is raised to 105 ℃; wherein, the consumption of the polymerization inhibitor hydroquinone is 1 to 10 percent of the mass of the itaconic acid;
after the esterification reaction is finished, dissolving the crude product by using dichloromethane, washing the crude product by using saturated saline water and deionized water for 3 times respectively, drying the crude product, and further purifying the collected organic phase by silica gel column chromatography to obtain light yellow liquid itaconic acid modified photoinitiator; wherein the developing agent in the silica gel column is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 2: 1.
The esterification reaction equation of the itaconic acid modified photoinitiator is as follows:
the invention has the beneficial effects that:
1. the method comprises the steps of introducing itaconic acid into Darocure2959(2 hydroxy-4- (2 hydroxyethoxy) -2-methyl propiophenone), and preparing a novel photoinitiator containing an initiating group and a polymerizable group by using unsaturated double bonds of the itaconic acid.
2. Due to the existence of itaconic acid unsaturated double bonds, the photoinitiator has the characteristics that fragments broken after illumination and unreacted initiators can be crosslinked and polymerized with resin and monomers in a system to generate macromolecules, and low mobility and low volatility are realized.
3. The itaconic acid modified photoinitiator has simple preparation process, easily obtained raw materials and easy realization of process production.
4. When the itaconic acid modified photoinitiator is used for an ultraviolet curing system containing a double-bond structure, the curing time of the system is less than 60 seconds under the irradiation of ultraviolet light with the power of 200-2000W, and the photoinitiator has good photoinitiation activity.
5. The Darocure2959 belongs to a photoinitiator with lower toxicity and is approved by the FDA in the United states to be a photoinitiator for food packaging, and the itaconic acid modified Darocure2959 photoinitiator has good photoinitiation activity and lower migration volatility, so the itaconic acid modified Darocure2959 photoinitiator is expected to replace Darocure2959 in fields with higher requirements on biological toxicity, such as food, medicine packaging coatings, contact biological medicine materials and the like.
Drawings
FIG. 1 shows the molecular structure of itaconic acid-modified photoinitiators (IAHHMP) of the present invention.
Detailed Description
Example 1
In N2Under protection, the water separator is arranged in the water tank,0.5g (0.0038mol) of itaconic acid, 0.05g of hydroquinone and 60mL of N, N-Dimethylformamide (DMF) are respectively added into a dry three-neck flask with a thermometer, after the itaconic acid is completely dissolved, 1.75g (0.0076mol) of 2 hydroxy-4- (2 hydroxyethoxy) -2-methyl propiophenone (HHMP) is added, the mixture is stirred uniformly, 0.05g of catalyst methane sulfonic acid is continuously added, and after the temperature is raised to 105 ℃, the temperature is kept and the heating reaction is continuously carried out for 6 hours.
After the esterification reaction is finished, dissolving the crude product by using 40mL of dichloromethane, washing the crude product by using 60mL of saturated saline water and 60mL of deionized water for 3 times respectively, drying the crude product, and further purifying the collected organic phase by silica gel column chromatography to obtain 1.83g of light yellow liquid itaconic acid modified photoinitiator, wherein the yield is 88.6%; wherein the developing agent in the silica gel column is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 2: 1.
Example 2
Preparing 1% of trihydroxymethyl triacrylate solution of IAHHMP and 2 hydroxy-4- (2 hydroxyethoxy) -2-methyl phenylpropanone (HHMP), respectively, coating on a glass slide, wherein the thickness of a film body is generally 30-35 μm, curing the film in the air by a portable curing machine, and setting the parameters of the curing machine to be 5.5cm from a lamp distance and 400W of power. The cured films were then cut into pieces, 0.075g each, and treated by extraction with 20mL of acetonitrile for three days under standard conditions, and subjected to the UV absorption test in exactly the same manner. . The relative mobility of IAHHMP to 2959 photoinitiator was calculated from the following formula.
c＝A/(ε×b)
R＝c(IAHHMP)/c(2959)
C is the specific concentration of the internal photoinitiator in the extract, and the unit is mol/L; a is the absorbance; ε represents the molar absorptivity, whose unit is L/(mol. cm); b is the cell thickness in cm; (IAHHMP) is the concentration of IAHHMP in the extract; c (2959) is the concentration of 2959 photoinitiator in the extract; r is the relative mobility of IAHHMP, and the experimental result is as follows: a (IAHHMP) is 0.1627, c (IAHHMP) is 6.75X 10-6 mol/L; a (2959) is 0.9752, c (2959) is 2.67X 10-5 mol/L; the mobility of IAHHMP is 25.96% of that of 2959, and the experimental result shows that the mobility of the new photoinitiator prepared by modifying Darocure2959 with itaconic acid is only about one fourth of that of Darocure2959, and the reduction is obvious.
Claims (1)
1. An itaconic acid modified photoinitiator and a preparation method thereof are characterized in that: the molecular structure of the itaconic acid modified photoinitiator is as follows:
the preparation method of the itaconic acid modified photoinitiator comprises the following steps:
itaconic acid and photoinitiator 2 hydroxy-4- (2 hydroxyethoxy) -2-methyl propiophenone are taken as raw materials, and the itaconic acid modified photoinitiator with a polymerizable structure is synthesized through esterification reaction, and the method comprises the following specific steps:
in N2Under protection, respectively adding itaconic acid, hydroquinone of a polymerization inhibitor and a solvent N, N-dimethylformamide into a dry three-neck flask provided with a condenser, a water separator and a thermometer, adding 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone after the itaconic acid is completely dissolved, continuously adding a catalyst methanesulfonic acid after stirring uniformly, and keeping the temperature to continuously heat and react for 6 hours after the temperature is raised to 105 ℃, wherein the consumption of the hydroquinone of the polymerization inhibitor is ~ 10 percent of the mass of the itaconic acid;
after the esterification reaction is finished, dissolving the crude product by using dichloromethane, washing the crude product by using saturated saline water and deionized water for 3 times respectively, drying the crude product, and further purifying the collected organic phase by silica gel column chromatography to obtain light yellow liquid itaconic acid modified photoinitiator; wherein the developing agent in the silica gel column is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 2: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113061409A (en) * | 2021-04-19 | 2021-07-02 | 昆山石梅新材料科技有限公司 | Acrylic adhesive resin and preparation method and application thereof |
| CN114478436A (en) * | 2022-03-14 | 2022-05-13 | 浙江扬帆新材料股份有限公司 | Polymerizable itaconic acid group-containing modified alpha-aminoketone photoinitiator and preparation method and application thereof |
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